Tris(trimethyl siloxy)silane vinylic monomers and uses thereof

ABSTRACT

The invention provides a TRIS-containing vinylic monomer which comprises one sole (meth)acryloyloxy group and a tris(trimethylsiloxy)silyl group covalently linked to the ethylenically-unsaturated group through a polyoxyethylene linker. The present invention is also related to a polymer, an actinically-crosslinkable silicone-containing prepolymer, a silicone hydrogel polymeric material, or a silicone hydrogel contact lens, which comprises monomeric units derived from a TRIS-containing vinylic monomer of the invention. In addition, the invention provides a method for making a TRIS-containing vinylic monomer of the invention.

The present invention is related to a class of tris(trimethylsiloxy)silane vinylic monomers with a polyoxyethylene segment and theiruses in making medical devices including contact lenses. In addition,the present invention is related to a method for producing this class oftris(trimethyl siloxy)silane vinylic monomers.

BACKGROUND

A vinylic monomer having a tris(trimethylsilyloxy)silyl (“TRIS”) group,such as, for example, tris(trimethylsilyloxy)silylpropyl acrylate,tris(trimethylsilyloxy)-silylpropyl methacrylate,tris(trimethylsilyloxy)-silylpropyl acryalmide,tris(trimethylsilyloxy)-silylpropyl methacrylamide,tris-(trimethylsiloxysilyl) propylvinyl carbamate, or the like, has beenwidely used in making silicone hydrogel contact lenses, as it canenhance the oxygen permeability of a lens material while giving the lenswith clarity and superior lens properties. Moreover, presence ofTRIS-containing vinylic monomers may also be important for dissipationof lens folding mark during lens handling. However, most ofTRIS-containing vinylic monomers used in the contact lens industryand/or on the market are generally hydrophobic, not compatible with thehydrophilic components of a silicone hydrogel lens formulation, and notsuitable for making water-based silicone hydrogel lens formulations. Inaddition, unpolymerized TRIS-containing vinylic monomers must be removedfrom molded lenses by using an organic solvent in a lens extractionprocess. Such lens extraction process increases the production cost andis not environmentally friendly.

Therefore, there is still a need for TRIS-containing vinylic monomerswhich have adequate solubility in water and can be used in anenvironmentally-friendly lens production process.

SUMMARY OF THE INVENTION

In one aspect, the invention provides a TRIS-containing vinylic monomer,which comprises one sole ethylenically unsaturated group and atris(trimethylsilyloxy)silyl group covalently linked to theethylenically-unsaturated group through a polyoxyethylene linker.

The present invention, in another aspect, provides a polymer which is apolymerization product of a polymerizable composition comprising aTRIS-containing vinylic monomer of the invention.

The present invention, in a further aspect, provides a method forproducing a TRIS-containing vinylic monomer of the invention. The methodcomprises the steps of reacting a polyoxyethylene (meth)acrylate with anisocyanatoalkyl tris(trimethylsiloxy)silane, in the presence or absenceof a solvent and in the presence of a catalyst.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing the ¹H-NMR spectrum of a preferredTRIS-containing vinylic monomer.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Generally, the nomenclatureused herein and the laboratory procedures are well known and commonlyemployed in the art. Conventional methods are used for these procedures,such as those provided in the art and various general references. Wherea term is provided in the singular, the inventors also contemplate theplural of that term. The nomenclature used herein and the laboratoryprocedures described below are those well known and commonly employed inthe art.

“About” as used herein means that a number referred to as “about”comprises the recited number plus or minus 1-10% of that recited number.

A “medical device” refers to a device having surfaces that contacttissue, blood, or other bodily fluids of patients in the course of theiroperation. Exemplary medical devices include: (1) extracorporeal devicesfor use in surgery such as blood oxygenators, blood pumps, bloodsensors, tubing used to carry blood and the like which contact bloodwhich is then returned to the patient; (2) prostheses implanted in ahuman or animal body such as vascular grafts, stents, pacemaker leads,heart valves, and the like that are implanted in blood vessels or in theheart; (3) devices for temporary intravascular use such as catheters,guide wires, and the like which are placed into blood vessels or theheart for purposes of monitoring or repair; and (4) ophthalmic devices.

An “ophthalmic device”, as used herein, refers to a contact lens (hardor soft), an intraocular lens, a corneal onlay, other ophthalmic devices(e.g., stents, glaucoma shunt, or the like) used on or about the eye orocular vicinity.

“Contact Lens” refers to a structure that can be placed on or within awearer's eye. A contact lens can correct, improve, or alter a user'seyesight, but that need not be the case. A contact lens can be of anyappropriate material known in the art or later developed, and can be asoft lens, a hard lens, or a hybrid lens. A “silicone hydrogel contactlens” refers to a contact lens comprising a silicone hydrogel material.

A “hydrogel” or “hydrogel material” refers to a polymeric material whichis insoluble in water, but can absorb at least 10 percent by weight ofwater when it is fully hydrated.

A “silicone hydrogel” refers to a silicone-containing hydrogel obtainedby copolymerization of a polymerizable composition comprising at leastone silicone-containing monomer or at least one crosslinkablesilicone-containing prepolymer.

“Hydrophilic,” as used herein, describes a material or portion thereofthat will more readily associate with water than with lipids.

A “vinylic monomer” refers to a compound that has one sole ethylenicallyunsaturated group and is soluble in a solvent.

The term “soluble”, in reference to a compound or material in a solvent,means that the compound or material can be dissolved in the solvent togive a solution with a concentration of at least about 1% by weight atroom temperature (i.e., a temperature of about 20° C. to about 30° C.).

The term “insoluble”, in reference to a compound or material in asolvent, means that the compound or material can be dissolved in thesolvent to give a solution with a concentration of less than 0.005% byweight at room temperature (as defined above).

As used in this application, the term “ethylenically unsaturated group”is employed herein in a broad sense and is intended to encompass anygroups containing at least one >C═C< group. Exemplary ethylenicallyunsaturated groups include without limitation (meth)acryloyl

allyl, vinyl, styrenyl, or other C═C containing groups.

As used in this application, the term “(meth)acrylamide” refers tomethacrylamide and/or acrylamide and the term “(meth)acrylate” refers tomethacrylate and/or acrylate.

As used herein, “actinically” in reference to curing, crosslinking orpolymerizing of a polymerizable composition, a prepolymer or a materialmeans that the curing (e.g., crosslinked and/or polymerized) isperformed by actinic irradiation, such as, for example, UV irradiation,ionizing radiation (e.g. gamma ray or X-ray irradiation), microwaveirradiation, and the like. Thermal curing or actinic curing methods arewell-known to a person skilled in the art.

As used in this application, the term “hydrophilic vinylic monomer”refers to a vinylic monomer capable of forming a homopolymer that iswater-soluble or can absorb at least 10 percent by weight of water atroom temperature.

As used in this application, the term “hydrophobic vinylic monomer”refers to a vinylic monomer which as a homopolymer typically yields apolymer that is insoluble in water and can absorb less than 10 percentby weight of water at room temperature.

As used in this application, “TRIS” refers to a radical of—Si—[OSi(CH₃)₃]₃, namely the tris(trimethylsilyloxy)silyl group.

A “prepolymer” refers to a starting polymer which contains two or moreethylenically unsaturated groups and can be cured (e.g., crosslinked)actinically or thermally to obtain a crosslinked polymer having amolecular weight much higher than the starting polymer.

As used in this application, the term “crosslinker” refers to a compoundor a polymer having at least two ethylenically unsaturated groups andbeing soluble in a solvent at room temperature. A “crosslinking agent”refers to a crosslinker having a molecular weight of about 700 Daltonsor less.

A “polysiloxane” refers to a compound containing one sole polysiloxanesegment of

in which R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀, independently of oneanother, are C₁-C₁₀ alkyl, C₁-C₄ alkyl- or C₁-C₄-alkoxy-substitutedphenyl, C₁-C₁₀ fluoroalkyl, C₁-C₁₀ fluoroether, C₆-C₁₈ aryl radical,-alk-(OCH₂CH₂)_(n1)'OR₁₁ in which alk is C₁-C₆-alkylene divalentradical, R₁₁ is hydrogen or C₁-C₅ alkyl and n1 is an integer from 1 to10, m1 and m2 independently of each other are an integer of from 0 to 50and (m1+m2) is from 1 to 100.

A “chain-extended polysiloxane” refers to a compound containing at leasttwo polysiloxane segments separated by a linkage.

A “polysiloxane-containing crosslinker” refers to a compound having atleast two ethylenically unsaturated groups and at least one polysiloxanesegment.

As used in this application, the term “polymer” means a material formedby polymerizing/crosslinking one or more monomers or prepolymers.

As used in this application, the term “molecular weight” of a polymericmaterial (including monomeric or macromeric materials) refers to theweight-average molecular weight unless otherwise specifically noted orunless testing conditions indicate otherwise.

The term “alkyl” refers to a monovalent radical obtained by removing ahydrogen atom from a linear or branched alkane compound. An alkyl group(radical) forms one bond with one other group in an organic compound.

The term “alkylene” or “alkane diradical” refers to a divalent radicalobtained by removing one hydrogen atom from an alkyl. An alkylene group(or radical) forms two bonds with other groups in an organic compound.

The term “cycloalkane diradical” refers to a divalent radical obtainedby removing two hydrogen atoms from a substituted or unsubstitutedcycloalkane. A cycloalkane diradical forms two bonds with other groupsin an organic compound.

In this application, the term “substituted” in reference to an alkylenedivalent radical or an alkyl radical or a cycloalkane means that thealkylene divalent radical or the alkyl radical or the cycloalkanediradical comprises at least one substituent which replaces one hydrogenatom of the alkylene or alkyl radical or cycloalkane diradical and isselected from the group consisting of hydroxyl, carboxyl, —NH₂,sulfhydryl, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio (alkyl sulfide),C₁-C₄ acylamino, C₁-C₄ alkylamino, di-C₁-C₄ alkylamino, halogen atom (Bror Cl), and combinations thereof.

The term “fluid” as used herein indicates that a material is capable offlowing like a liquid.

As used herein, the term “multiple” refers to three or more.

A free radical initiator can be either a photoinitiator or a thermalinitiator. A “photoinitiator” refers to a chemical that initiates freeradical crosslinking/polymerizing reaction by the use of light. A“thermal initiator” refers to a chemical that initiates radicalcrosslinking/polymerizing reaction by the use of heat energy.

A “UV-absorbing vinylic monomer” refers to a compound comprising anethylenically-unsaturated group and a UV-absorbing moiety which canabsorb or screen out UV radiation in the range from 200 nm to 400 nm asunderstood by a person skilled in the art.

A “spatial limitation of actinic radiation” refers to an act or processin which energy radiation in the form of rays is directed by, forexample, a mask or screen or combinations thereof, to impinge, in aspatially restricted manner, onto an area having a well definedperipheral boundary. A spatial limitation of UV radiation is obtained byusing a mask or screen having a radiation (e.g., UV) permeable region, aradiation (e.g., UV) impermeable region surrounding theradiation-permeable region, and a projection contour which is theboundary between the radiation-impermeable and radiation-permeableregions, as schematically illustrated in the drawings of U.S. Pat. No.6,800,225 (FIGS. 1-11), and U.S. Pat. No. 6,627,124 (FIGS. 1-9), U.S.Pat. No. 7,384,590 (FIGS. 1-6), and U.S. Pat. No. 7,387,759 (FIGS. 1-6),all of which are incorporated by reference in their entireties. The maskor screen allows to spatially projects a beam of radiation (e.g., UVradiation) having a cross-sectional profile defined by the projectioncontour of the mask or screen. The projected beam of radiation (e.g., UVradiation) limits radiation (e.g., UV radiation) impinging on alens-forming material located in the path of the projected beam from thefirst molding surface to the second molding surface of a mold. Theresultant contact lens comprises an anterior surface defined by thefirst molding surface, an opposite posterior surface defined by thesecond molding surface, and a lens edge defined by the sectional profileof the projected UV beam (i.e., a spatial limitation of radiation). Theradiation used for the crosslinking is radiation energy, especially UVradiation, gamma radiation, electron radiation or thermal radiation, theradiation energy preferably being in the form of a substantiallyparallel beam in order on the one hand to achieve good restriction andon the other hand efficient use of the energy.

The intrinsic “oxygen permeability”, Dk, of a material is the rate atwhich oxygen will pass through a material. As used in this application,the term “oxygen permeability (Dk)” in reference to a hydrogel (siliconeor non-silicone) or a contact lens means a measured oxygen permeability(Dk) which is corrected for the surface resistance to oxygen flux causedby the boundary layer effect according to the procedures shown inExamples hereinafter. Oxygen permeability is conventionally expressed inunits of barrers, where “barrer” is defined as [(cm³oxygen)(mm)/(cm²)(sec)(mm Hg)]×10⁻¹⁰.

The “oxygen transmissibility”, Dk/t, of a lens or material is the rateat which oxygen will pass through a specific lens or material with anaverage thickness of t [in units of mm] over the area being measured.Oxygen transmissibility is conventionally expressed in units ofbarrers/mm, where “barrers/mm” is defined as [(cm³ oxygen)/(cm²)(sec)(mmHg)]×10⁻⁹.

The term “water soluble or processable” in reference to aTRIS-containing vinylic monomer of the invention means that the vinylicmonomer has a water solubility and/or dispersity of from about 1% toabout 70% by weight at room temperature (about 22° C. to about 28° C.).

The term “water solubility and/or dispersity” in reference to aTRIS-containing vinylic monomer of the invention means the concentration(weight percentage) of the TRIS-containing vinylic monomer dissolvedand/or dispersed in water at room temperature (about 22° C. to about 28°C.) to form a transparent aqueous solution or a slightly hazy aqueoussolution having a light transmissibility of 85% or greater in the rangebetween 400 to 700 nm.

A “coupling reaction” in this patent application is intended to describeany reaction between a pair of matching functional groups in thepresence or absence of a coupling agent to form covalent bonds orlinkages under various reaction conditions well known to a personskilled in the art, such as, for example, oxidation-reductionconditions, dehydration condensation conditions, addition conditions,substitution (or displacement) conditions, Diels-Alder reactionconditions, cationic crosslinking conditions, ring-opening conditions,epoxy hardening conditions, and combinations thereof.

Non-limiting examples of coupling reactions under various reactionconditions between a pair of matching co-reactive functional groupsselected from the group preferably consisting of amino group (—NHR′ inwhich R′ is H or C₁-C₄ alkyl), hydroxyl group, carboxyl group, acidhalide group (—COX, X═Cl, Br, or I), acid anhydrate group, aldehydegroup, azlactone group, isocyanate group, epoxy group, aziridine group,and thiol group, are given below for illustrative purposes. An aminogroup reacts with aldehyde group to form a Schiff base which may furtherbe reduced; an amino group —NHR′ reacts with an acid chloride or bromidegroup or with an acid anhydride group to form an amide linkage (—CO—NR′—with R′ as defined above); an amino group —NHR′ reacts with anisocyanate group to form a urea linkage (—NR′—C(O)—NH— with R′ asdefined above); an amino group —NHR′ reacts with an epoxy or aziridinegroup to form an amine bond (—C—NR′— with R′ as defined above); an aminogroup —NHR′ reacts (ring-opening) with an azlactone group to form analkylene-diamido linkage (—C(O)NH-alkylene-C(O)NR′— with R′ as definedabove); an amino group —NHR′ reacts with a carboxylic acid group in thepresence of a coupling agent—carbodiimide (e.g.,1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC),N,N′-dicyclohexylcarbodiimide (DCC),1-cylcohexyl-3-(2-morpholinoethyl)carbodiimide, diisopropylcarbodiimide, or mixtures thereof) to form an amide linkage; an aminogroup —NHR′ reacts with a N-hydroxysuccinimide ester group to form anamide linkage; a hydroxyl reacts with an isocyanate to form a urethanelinkage; a hydroxyl reacts with an epoxy or aziridine to form an etherlinkage (—O—); a hydroxyl reacts with an acid chloride or bromide groupor with an acid anhydride group to form an ester linkage; an hydroxylgroup reacts with an azlactone group in the presence of a catalyst toform an amidoalkylenecarboxy linkage (—C(O)NH-alkylene-C(O)—O—); acarboxyl group reacts with an epoxy group to form an ester bond; a thiolgroup (—SH) reacts with an isocyanate to form a thiocarbamate linkage(—N—C(O)—S—); a thiol group reacts with an epoxy or aziridine to form athioether linkage (—S—); a thiol group reacts with an acid chloride orbromide group or with an acid anhydride group to form a thiolesterlinkage; a thiol group reacts with an azlactone group in the presence ofa catalyst to form a linkage (—C(O)NH—CR₃R₄—(CH₂)p-C(O)—S—). A thiolgroup reacts with a vinyl group based on thiol-ene reaction underthiol-ene reaction conditions to form a thioether linakge (—S—). A thiolgroup reacts with an acryloyl or methacryloyl group based on MichaelAddition under appropriate reaction conditions to form a thioetherlinkage.

It is also understood that coupling agents with two reactive functionalgroups may be used in the coupling reactions. A coupling agent havingtwo reactive functional groups can be a diisocyanate, a di-acid halide,a di-carboxylic acid compound, a di-acid halide compound, a di-azlactonecompound, a di-epoxy compound, a diamine, or a diol. A person skilled inthe art knows well to select a coupling reaction (e.g., anyone describedabove in this application) and conditions thereof to prepare apolysiloxane terminated with one or more ethylenically unsaturatedgroups. For example, a diisocyanate, di-acid halide, di-carboxylic acid,di-azlactone, or di-epoxy compound can be used in the coupling of twohydroxyl, two amino groups, two carboxyl groups, two epoxy groups, orcombination thereof; a diamine or dihydroxyl compound can be used in thecoupling of two isocyanate, epoxy, aziridine, carboxylic acid, acidhalide or azlactone groups or combinations thereof.

Any suitable C₄-C₂₄ diisocyanates can be used in the invention. Examplesof preferred diisocyanates include without limitation isophoronediisocyanate, hexamethyl-1,6-diisocyanate, 4,4′-dicyclohexylmethanediisocyanate, toluene diisocyanate, 4,4′-diphenyl diisocyanate,4,4′-diphenylmethane diisocyanate, p-phenylene diisocyanate,1,4-phenylene 4,4′-diphenyl diisocyanate, 1,3-bis-(4,4′-isocyantomethyl) cyclohexane, cyclohexane diisocyanate, and combinations thereof.

Any suitable diamines can be used in the invention. An organic diaminecan be a linear or branched C₂-C₂₄ aliphatic diamine, a C₅-C₂₄cycloaliphatic or aliphatic-cycloaliphatic diamine, or a C₆-C₂₄ aromaticor alkyl-aromatic diamine. A preferred organic diamine isN,N′-bis(hydroxyethyl)ethylenediamine, N,N′-dimethylethylenediamine,ethylenediamine, N,N′-dimethyl-1,3-propanediamine,N,N′-diethyl-1,3-propanediamine, propane-1,3-diamine,butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, andisophorone diamine.

Any suitable diacid halides can be used in the invention. Examples ofpreferred diacid halide include without limitations fumaryl chloride,suberoyl chloride, succinyl chloride, phthaloyl chloride, isophthaloylchloride, terephthaloyl chloride, sebacoyl chloride, adipoyl chloride,trimethyladipoyl chloride, azelaoyl chloride, dodecanedioic acidchloride, succinic chloride, glutaric chloride, oxalyl chloride, dimeracid chloride, and combinations thereof.

Any suitable di-epoxy compounds can be used in the invention. Examplesof preferred di-epoxy compounds are neopentyl glycol diglycidyl ether,1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether,glycerol diglycidyl ether, ethylene glycol diglycidyl ether, diethyleneglycol diglycidyl ether, polyethylene glycol diglycidyl ether, propyleneglycol diglycidyl ether, dipropylene glycol diglycidyl ether, andcombinations thereof. Such di-epoxy compounds are available commercially(e.g., those DENACOL series di-epoxy compounds from Nagase ChemteXCorporation).

Any suitable C₂-C₂₄ diols (i.e., compounds with two hydroxyl groups) canbe used in the invention. Examples of preferred diols include withoutlimitation ethylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, polyethylene glycol, propylene glycol,1,4-butanediol, various pentanediols, various hexanediols, variouscyclohexanediols, and combination thereof.

Any suitable C₃-C₂₄ di-carboxylic acid compounds can be used in theinvention. Examples of preferred di-carboxylic acid compounds includewithout limitation a linear or branched C₃-C₂₄ aliphatic dicarboxylicacid, a C₅-C₂₄ cycloaliphatic or aliphatic-cycloaliphatic dicarboxylicacid, a C₆-C₂₄ aromatic or araliphatic dicarboxylic acid, a dicarboxylicacid which contains amino or imido groups or N-heterocyclic rings, andcombinations thereof. Examples of suitable aliphatic dicarboxylic acidsare: oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, pimelic acid, suberic acid, azelaic acid, sebacic acid,undecanedioic acid, dodecanedioic acid, dimethylmalonic acid,octadecylsuccinic acid, trimethyladipic acid, and dimeric acids(dimerisation products of unsaturated aliphatic carboxylic acids, suchas oleic acid). Examples of suitable cycloaliphatic dicarboxylic acidsare: 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylicacid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and1,4-dicarboxylmethylcyclohexane, 4,4′-dicyclohexyldicarboxylic acid.Examples of suitable aromatic dicarboxylic acids are: terephthalic acid,isophthalic acid, o-phthalic acid, 1,3-, 1,4-, 2,6- or2,7-naphthalenedicarboxylic acids, 4,4′-diphenyldicarboxylic acid,4,4′-diphenylsulphone-dicarboxylic acid,1,1,3-trimethyl-5-carboxyl-3-(p-carboxyphenyl)-indane, 4,4′-diphenylether-dicarboxylic acid, bis-p-(carboxylphenyl)-methane.

Any suitable C₁₀-C₂₄ di-azlactone compounds can be used in theinvention. Examples of such diazlactone compounds are those described inU.S. Pat. No. 4,485,236 (herein incorporated by reference in itsentirety).

The reactions conditions for the above described coupling reactions aretaught in textbooks and are well known to a person skilled in the art.

As used in this application, the term “ethylenically functionalized” inreference to a compound or polymer or copolymer having one or morereactive functional groups (e.g., amine, hydroxyl, carboxyl, isocyanate,anhydride, and/or epoxy groups) means a process or product thereof inwhich one or more ethylenically unsaturated groups are covalentlyattached to the functional groups of the compound or polymer orcopolymer by reacting an ethylenically functionalizing vinylic monomerwith the compound or polymer or copolymer under coupling reactionconditions.

An “ethylenically functionalizing vinylic monomer” throughout of thispatent application refers to a vinylic monomer having one reactivefunctional group capable of participating in a coupling (orcrosslinking) reaction known to a person skilled in the art. Examples ofethylenically-functionalizing vinylic monomers include withoutlimitation C₂ to C₆ hydroxylalkyl (meth)acrylate, C₂ to C₆ hydroxyalkyl(meth)acrylamide, allylalcohol, allylamine, amino-C₂-C₆ alkyl(meth)acrylate, C₁-C₆ alkylamino-C₂-C₆ alkyl (meth)acrylate, vinylamine,amino-C₂-C₆ alkyl (meth)acrylamide, C₁-C₃ alkylamino-C₂-C₆ alkyl(meth)acrylamide, acrylic acid, C₁-C₄ alkylacrylic acid (e.g.,methacrylic ethylacrylic acid, propylacrylic acid, butylacrylic acid),N-[tris(hydroxymethyl)-methyl]acrylamide, N,N-2-acrylamidoglycolic acid,beta methyl-acrylic acid (crotonic acid), alpha-phenyl acrylic acid,beta-acryloxy propionic acid, sorbic acid, angelic acid, cinnamic acid,1-carobxy-4-phenyl butadiene-1,3, itaconic acid, citraconic acid,mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaricacid, aziridinyl C₁-C₁₂ alkyl (meth)acrylate (e.g., 2-(1-aziridinyl)ethyl (meth)acrylate, 3-(1-aziridinyl) propyl (meth)acrylate,4-(1-aziridinyl) butyl (meth)acrylate, 6-(1-aziridinyl) hexyl(meth)acrylate, or 8-(1-aziridinyl) octyl (meth)acrylate), glycidyl(meth)acrylate, vinyl glycidyl ether, allyl glycidyl ether,(meth)acryloyl halide groups (CH₂═CH—COX or CH₂═CCH₃—COX, X═Cl or Br),N-hydroxysuccinimide ester of (meth)acrylic acid, C₁ to C₆isocyanatoalkyl (meth)acrylate, azlactone-containing vinylic monomers(e.g., 2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one,2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one,2-vinyl-4-methyl-4-ethyl-1,3-oxazolin-5-one,2-isopropenyl-4-methyl-4-butyl-1,3-oxazolin-5-one,2-vinyl-4,4-dibutyl-1,3-oxazolin-5-one,2-isopropenyl-4-methyl-4-dodecyl-1,3-oxazolin-5-one,2-isopropenyl-4,4-diphenyl-1,3-oxazolin-5-one,2-isopropenyl-4,4-pentamethylene-1,3-oxazolin-5-one,2-isopropenyl-4,4-tetramethylene-1,3-oxazolin-5-one,2-vinyl-4,4-diethyl-1,3-oxazolin-5-one,2-vinyl-4-methyl-4-nonyl-1,3-oxazolin-5-one,2-isopropenyl-4-methyl-4-phenyl-1,3-oxazolin-5-one,2-isopropenyl-4-methyl-4-benzyl-1,3-oxazolin-5-one,2-vinyl-4,4-pentamethylene-1,3-oxazolin-5-one, and2-vinyl-4,4-dimethyl-1,3-oxazolin-6-one, with2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one (VDMO) and2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one (IPDMO) as preferredazlactone-containing vinylic monomers), and combinations thereof.

In general, the invention is directed to a class of TRIS-containingvinylic monomers and uses in preparing a polymer (preferably a siliconehydrogel material), and a medical device (preferably silicone hydrogelcontact lenses). A TRIS-containing vinylic monomer of the inventioncomprises: one sole (meth)acryloyloxy group; one soletris(trimethylsilyloxy)silyl group; and one polyoxyethylene-containinglinkage between the (meth)acryloyloxy group and thetris(trimethylsilyloxy)silyl group. A TRIS-containing vinylic monomer ofthe invention can be tailored to have a desired solubility (ordispersity) in a desired solvent, e.g., water or any one in a very broadrange of solvents, by varying the molecular mass of polyoxyethylenesegment. It can be used in a manufacturing process for making siliconehydrogel contact lenses in a more environmentally-friendly manner (e.g.,using a water-based lens formulation and/or using water as solvent inlens extraction process).

The present invention, in one aspect, provides a TRIS-containing vinylicmonomer being represented by formula (I)

in which: q1 is an integer of from 6 to 20; R₁ is hydrogen or methyl; R₂is a diradical of an alkane or cycloalkane which comprises up to 20carbon atoms and may have one or more ether, thio, amine, carbonyl, oramido linkages in the main chain.

A TRIS-containing vinylic monomers of formula (I) can be prepared from apolyoxyethylene (meth)acrylate and an isocyanatoalkyl tris(trimethylsiloxy)silane. The hydroxyl group of a polyoxyethylene (meth)acrylate(CH₂═CH—CO—(OCH₂CH₂)_(n)—OH or CH₂═CCH₃—CO—(OCH₂CH₂)_(n)—OH) can reactwith the isocyanate group of an isocyanatoalkyl tris(trimethylsiloxy)silane, in the presence of a catalyst (e.g., amine catalyst, suchas triethylamine; tin catalysts, such as dibutyltin dilaurate; irocatalysts, such as tris(2,4-pentanedionate iron(III); or the like) toform a urethane linkage, as described below.

In a preferred embodiment, a TRIS-containing vinylic monomer of formula(I) has a water solubility or dispersibility of at least about 5%,preferably at least about 10%, more preferably at least about 20% byweight in water.

A TRIS-containing vinylic monomer of formula(I) as defined above canfind use in preparing a polymer, preferably a silicone-containingactinically-crosslinkable prepolymer or a silicone hydrogel polymericmaterial, which is another aspect of the invention.

In another aspect, the invention is related to a polymer comprisingmonomeric units derived from a TRIS-containing vinylic monomer offormula (I) as defined above.

In this aspect of the invention, a polymer can be a copolymer soluble orinsoluble in a solvent, preferably an actinically-crosslinkableprepolymer or a silicone hydrogel material.

A person skilled in the art knows how to prepare a polymer, anactinically-crosslinkable silicone-containing prepolymer, or a siliconehydrogel material from a polymerizable composition according to anyknown free-radical polymerization mechanism. The polymerizablecomposition for preparing a polymer, an actinically-crosslinkablesilicone containing prepolymer (i.e., an intermediary copolymer for theprepolymer), or a silicone hydrogel polymeric material of the inventioncan be a melt, a solventless liquid in which all necessary componentsare blended together, or a solution in which all necessary component isdissolved in an inert solvent, such as water, an organic solvent, ormixture thereof, as known to a person skilled in the art.

Example of suitable solvents includes without limitation, water,tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycolmethyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone,methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethyleneglycol methyl ether, ethylene glycol phenyl ether, propylene glycolmethyl ether, propylene glycol methyl ether acetate, dipropylene glycolmethyl ether acetate, propylene glycol n-propyl ether, dipropyleneglycol n-propyl ether, tripropylene glycol n-butyl ether, propyleneglycol n-butyl ether, dipropylene glycol n-butyl ether, tripropyleneglycol n-butyl ether, propylene glycol phenyl ether dipropylene glycoldimetyl ether, polyethylene glycols, polypropylene glycols, ethylacetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate,i-propyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol,menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol,3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol,2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, tert-butanol,tert-amyl, alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol,3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol,3,7-dimethyl-3-octanol, 1-chloro-2-methyl-2-propanol,2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2-methyl-2-nonanol,2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol,4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol,3-methyl-3-nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol,3-ethyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4-heptanol,4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol,1-methylcyclopentanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol,3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol,2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol,2-methyl-1-phenyl-2-propanol and 3-ethyl-3-pentanol,1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amyl alcohol, isopropanol,1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethyl formamide,dimethyl acetamide, dimethyl propionamide, N-methyl pyrrolidinone, andmixtures thereof.

The copolymerization of a polymerizable composition for preparing apolymer, an actinically-crosslinkable silicone containing prepolymer(i.e., an intermediary copolymer for the prepolymer), or a siliconehydrogel polymeric material of the invention may be inducedphotochemically or thermally.

Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone,a benzoylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and Darocurand Irgacure types, preferably Darocur 1173®, Irgacure 369®, Irgacure379®, and Irgacure 2959®. Examples of benzoylphosphine oxide initiatorsinclude 2,4,6-trimethylbenzoyldiphenylophosphine oxide (TPO);bis-(2,6-dichlorobenzoyI)-4-N-propylphenylphosphine oxide; andbis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide. Reactivephotoinitiators which can be incorporated, for example, into a macromeror can be used as a special monomer are also suitable. Examples ofreactive photoinitiators are those disclosed in EP 632 329, hereinincorporated by reference in its entirety. The polymerization can thenbe triggered off by actinic radiation, for example light, in particularUV light of a suitable wavelength. The spectral requirements can becontrolled accordingly, if appropriate, by addition of suitablephotosensitizers.

Suitable thermal polymerization initiators are known to the skilledartisan and comprise, for example peroxides, hydroperoxides,azo-bis(alkyl- or cycloalkylnitriles), persulfates, percarbonates ormixtures thereof. Examples are benzoylperoxide, tert.-butyl peroxide,di-tert.-butyl-diperoxyphthalate, tert.-butyl hydroperoxide,azo-bis(isobutyronitrile) (Al BN), 1,1-azodiisobutyramidine,1,1′-azo-bis (1-cyclohexanecarbonitrile),2,2′-azo-bis(2,4-dimethylvaleronitrile) and the like. The polymerizationis carried out conveniently in an above-mentioned solvent at elevatedtemperature, for example at a temperature of from 25 to 100° C. andpreferably 40 to 80° C. The reaction time may vary within wide limits,but is conveniently, for example, from 1 to 24 hours or preferably from2 to 12 hours. It is advantageous to previously degas the components andsolvents used in the polymerization reaction and to carry out saidcopolymerization reaction under an inert atmosphere, for example under anitrogen or argon atmosphere.

Generally, a polymer of the invention is obtained by polymerizingthermally or actinically a polymerizable composition including aTRIS-containing vinylic monomer of formula (I) as defined above and oneor more polymerizable components selected from the group consisting of ahydrophilic vinylic monomer, a hydrophobic vinylic monomer, apolysiloxane-containing vinylic monomer, a polysiloxane-containingcrosslinker, a non-silicone crosslinker, a hydrophilic prepolymer, aUV-absorbing vinylic monomer, and combinations thereof. Variousembodiments of all of the above-described polymerizable components arediscussed below.

In accordance with the invention, any suitable hydrophilic vinylicmonomers can be used in a polymerizable composition for preparing apolymer of the invention. Examples of preferred hydrophilic vinylicmonomers include without limitation N-vinylpyrrolidone, N,N-dimethyl(meth)acrylamide, (meth)acrylamide, hydroxylethyl (meth)acrylamide,hydroxyethyl (meth)acrylate, glycerol methacrylate (GMA), polyethyleneglycol (meth)acrylate, polyethylene glycol C₁-C₄-alkyl ether(meth)acrylate having a weight average molecular weight of up to 1500,N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide,N-vinyl-N-methyl acetamide, N-methyl-3-methylene-2-pyrrolidone,1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone,1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone,5-ethyl-3-methylene-2-pyrrolidone, (meth)acrylic acid, ethylacrylicacid, and combinations thereof.

Any suitable hydrophobic vinylic monomers can be used in a polymerizablecomposition for making a polymer of the invention. By incorporating acertain amount of hydrophobic vinylic monomer in a monomer mixture, themechanical properties (e.g., modulus of elasticity) of the resultantpolymer may be improved. Examples of preferred hydrophobic vinylicmonomers include methylacrylate, ethyl-acrylate, propylacrylate,isopropylacrylate, cyclohexylacrylate, 2-ethylhexylacrylate,methylmethacrylate, ethylmethacrylate, propylmethacrylate, vinylacetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene,chloroprene, vinyl chloride, vinylidene chloride, acrylonitrile,1-butene, butadiene, methacrylonitrile, vinyl toluene, vinyl ethylether, perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate,isobornyl methacrylate, trifluoroethyl methacrylate,hexafluoro-isopropyl methacrylate, hexafluorobutyl methacrylate.

Any suitable polysiloxane-containing vinylic monomer (each comprising atleast one polysiloxane segment and one sole ethylenically unsaturatedgroup) can be used in a polymerizable composition for preparing apolymer of the invention. Preferred examples of such vinylic monomersare mono-(meth)acrylated polydimethylsiloxanes of various molecularweight (e.g., mono-3-methacryloxypropyl terminated, mono-C₁-C₄ alkylterminated polydimethylsiloxane, ormono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-C₁-C₄alkyl terminated polydimethylsiloxane). Alternatively, monoethylenicallyfunctionalized polysiloxanes can be obtained by ethylenicallyfunctionalizing of a monofunctionalized polysiloxanes (i.e., with onesole terminal functional group, such as, e.g., —NH₂, —OH, —COOH, epoxygroup, halide, etc.) as described above. Suitable monofunctionalizedpolysiloxanes are commercially available, e.g., from Aldrich, ABCR GmbH& Co., Fluorochem, or Gelest, Inc, Morrisville, Pa.

Any suitable polysiloxane-containing crosslinkers (each of whichcomprises at least one polysiloxane segment and at least twoethylenically unsaturated groups) can be used in a polymerizablecomposition for preparing a polymer of the invention. Examples ofpolysiloxane-containing crosslinkers include without limitation,bis-(meth)acrylated polydimethylsiloxanes; bis-vinylcarbonate-terminated polydimethylsiloxanes; bis-vinylcarbamate-terminated polydimethylsiloxane; bis-vinyl terminatedpolydimethylsiloxanes; bis-(meth)acrylamide-terminatedpolydimethylsiloxanes; bis-3-methacryloxy-2-hydroxypropyloxypropylpolydimethylsiloxane;N,N,N′,N′-tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane;polysiloxane or chain-extended polysiloxane crosslinkers selected fromthe group consisting of Macromer A, Macromer B, Macromer C, and MacromerD described in U.S. Pat. No. 5,760,100 (herein incorporated by referencein its entirety); the reaction products of glycidyl (meth)acrylate withbis-aminoalkyl-terminated or bis-hydroxyalkoxyalkyl terminatedpolydimethylsiloxanes; the reaction products of hydroxy-containing oramino-containing vinylic monomer with bis-epoxyalkoxyalkyl-terminatedpolydimethylsiloxanes; polysiloxane-containing crosslinkers disclosed inU.S. Pat. Nos. 4,136,250, 4,153,641, 4,182,822, 4,189,546, 4,259,467,4,260,725, 4,261,875, 4,343,927, 4,254,248, 4,355,147, 4,276,402,4,327,203, 4,341,889, 4,486,577, 4,543,398, 4,605,712, 4,661,575,4,684,538, 4,703,097, 4,833,218, 4,837,289, 4,954,586, 4,954,587,5,010,141, 5,034,461, 5,070,170, 5,079,319, 5,039,761, 5,346,946,5,358,995, 5,387,632, 5,416,132, 5,451,617, 5,486,579, 5,962,548,5,981,675, 6,039,913, 6,762,264, 7,091,283, 7,238,750, 7,268,189,7,566,754, 7,956,135, 8,071,696, 8,071,703, 8,071,658, 8,048,968, 8,283,429, 8,263,679, 8,044,111, and 8,211,955 and in published US patentapplication Nos. 2008/0015315 A1, 2010/0120939 A1, 2010/0298446 A1,2010/0296049 A1, 2011/0063567 A1, 2012/0088843 A1, 2012/0088844 A1,2012/0029111 A1, and 2012/0088861 A1 (herein incorporated by referencein their entireties).

Any suitable non-silicone crosslinkers can be used in a polymerizablecomposition for preparing a polymer of the invention. Examples ofpreferred non-silicone crosslinkers include without limitationtetraethyleneglycol di-(meth)acrylate, triethyleneglycoldi-(meth)acrylate, ethyleneglycol di-(meth)acrylate, diethyleneglycoldi-(meth)acrylate, bisphenol A dimethacrylate, vinyl methacrylate,ethylenediamine di(meth)acrylamide, glycerol dimethacrylate,allyl(meth)acrylate, N,N′-methylenebis(meth)acrylamide,N,N′-ethylenebis(meth)acrylamide, N,N′-dihydroxyethylenebis(meth)acrylamide, a product of diamine (preferably selected from thegroup consisting of N,N′-bis(hydroxyethyl)-ethylenediamine,N,N′-dimethylethylenediamine, ethylenediamine,N,N′-dimethyl-1,3-propanediamine, N,N′-diethyl-1,3-propanediamine,propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine,hexamethylenediamine, isophorone diamine, and combinations thereof) andepoxy-containing vinylic monomer (prepferrably selected from the groupconsisting of glycidyl (meth)acrylate, vinyl glycidyl ether, allylglycidyl ether, and combinations thereof), combinations thereof. A morepreferred crosslinker to be used in the preparation of a polymer, anactinically-crosslinkable silicone containing prepolymer, or a siliconehydrogel polymeric material of the invention is a hydrophiliccrosslinker selected from the group consisting of tetra(ethyleneglycol)diacrylate, tri(ethyleneglycol) diacrylate, ethyleneglycol diacrylate,di(ethyleneglycol) diacrylate, glycerol dimethacrylate,allyl(meth)acrylate, N,N′-methylene bis(meth)acrylamide, N,N′-ethylenebis(meth)acrylamide, N,N′-dihydroxyethylene bis(meth)acrylamide, andcombinations thereof.

Examples of hydrophilic prepolymers with multiple acryloyl ormethacryloyl groups include, but are not limited to, a water-solublecrosslinkable poly(vinyl alcohol) prepolymer described in U.S. Pat. Nos.5,583,163 and 6,303,687; a water-soluble vinyl group-terminatedpolyurethane prepolymer described in U.S. Patent Application PublicationNo. 2004/0082680; derivatives of a polyvinyl alcohol, polyethyleneimineor polyvinylamine, which are disclosed in U.S. Pat. No. 5,849,841; awater-soluble crosslinkable polyurea prepolymer described in U.S. Pat.No. 6,479,587 and in U.S. Published Application No. 2005/0113549;crosslinkable polyacrylamide; crosslinkable statistical copolymers ofvinyl lactam, MMA and a comonomer, which are disclosed in EP 655,470 andU.S. Pat. No. 5,712,356; crosslinkable copolymers of vinyl lactam, vinylacetate and vinyl alcohol, which are disclosed in EP 712,867 and U.S.Pat. No. 5,665,840; polyether-polyester copolymers with crosslinkableside chains which are disclosed in EP 932,635 and U.S. Pat. No.6,492,478; branched polyalkylene glycol-urethane prepolymers disclosedin EP 958,315 and U.S. Pat. No. 6,165,408; polyalkyleneglycol-tetra(meth)acrylate prepolymers disclosed in EP 961,941 and U.S.Pat. No. 6,221,303; and crosslinkable polyallylamine gluconolactoneprepolymers disclosed in International Application No. WO 2000/31150 andU.S. Pat. No. 6,472,489.

Any suitable UV-absorbing vinylic monomers can be used in apolymerizable composition for preparing a polymer of the invention.Preferred UV absorbing vinylic monomers include without limitation2-(2-hydroxy-5-vinylphenyI)-2H-benzotriazole,2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole,2-(2-hydroxy-3-methacrylamido methyl-5-tert octylphenyl)benzotriazole,2-(2′-hydroxy-5′-methacrylamidophenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methacrylamidophenyl)-5-methoxybenzotriazole,2-(2′-hydroxy-5′-methacryloxypropyl-3′-t-butyl-phenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methacryloxyethylphenyl)benzotriazole,2-(2′-hydroxy-5′-methacryloxypropylphenyl) benzotriazole,2-hydroxy-4-acryloxy alkoxy benzophenone, 2-hydroxy-4-methacryloxyalkoxy benzophenone, allyl-2-hydroxybenzophenone,2-hydroxy-4-methacryloxy benzophenone. In accordance with the invention,the polymerizable composition comprises about 0.2% to about 5.0%,preferably about 0.3% to about 2.5%, more preferably about 0.5% to about1.8%, by weight of a UV-absorbing agent.

In a preferred embodiment, a polymer of the invention is asilicone-containing actinically-crosslinkable prepolymer, whichpreferably comprises: (1) monomeric units derived from a TRIS-containingvinylic monomer of formula (I) as defined above; (2) crosslinking unitsderived from at least one polysiloxane-containing crosslinker asdescribed above and/or polysiloxane units derived from apolysiloxane-containing vinylic monomer as described above, (3)hydrophilic units derived from at least one hydrophilic vinylic monomeras described above; (4) polymerizable units derived from a chaintransfer agent having a first reactive functional group other than thiolgroup and/or a vinylic monomer having a second reactive functional groupother than ethylenically-unsaturated group, wherein the polymerizableunits each comprise an ethylenically unsaturated group covalentlyattached to one polymerizable unit through the first or second reactivefunctional group; (5) optionally non-silicone crosslinking units derivedfrom at least one non-silicone crosslinker as described above; and (6)optionally UV-absorbing units derived from a UV-absorbing vinylicmonomer as described above. Such a prepolymer is capable of beingactinically crosslinked, in the absence of one or more vinylic monomers,to form a silicone hydrogel contact lens having a water content of fromabout 20% to about 75% (preferably from about 25% to about 70%, morepreferably from about 30% to about 65%) by weight when fully hydrated,and an oxygen permeability (Dk) of at least about 40 barrers (preferablyat least about 50 barrers, more preferably at least about 60 barrers,and even more preferably at least about 70 barrers). Preferably, such aprepolymer is water soluble or processable and has a high watersolubility or dispersibility of at least about 5%, preferably at leastabout 10%, more preferably at least about 20% by weight in water. Anactinically-crosslinkable silicone-containing prepolymer of theinvention can find particular use in preparing silicone hydrogelophthalmic lenses, in particular contact lenses.

Such a prepolymer is obtained by first polymerizing a polymerizablecomposition including all polymerizable components specified above, toform an intermediary copolymer and then by ethylenically functionalizingthe intermediary copolymer with an ethylenically functionalizing vinylicmonomer having a third reactive functional group capable of reactingwith the first and/or second reactive functional group to form a linkagein a coupling reaction in the presence or absence of a coupling agent toform the prepolymer, wherein the first, second and third reactivefunctional groups independent of one another are selected from the groupconsisting of amino group, hydroxyl group, carboxyl group, acid halidegroup, azlactone group, isocyanate group, epoxy group, aziridine group,and combination thereof. The general procedures for preparingamphiphilic prepolymers are disclosed in U.S. Pat. Nos. 6,039,913,6,043,328, 7,091,283, 7,268,189 and 7,238,750, 7,521,519, 8,071,703,8,044,111, and 8,048,968; in US patent application publication Nos. US2008-0015315 A1, US 2008-0143958 A1, US 2008-0143003 A1, US 2008-0234457A1, US 2008-0231798 A1, 2010/0120939 A1, 2010/0298446 A1, 2012/0088843A1, 2012/0088844 A1, and 2012/0088861 A1; all of which are incorporatedherein by references in their entireties.

In accordance with the invention, the polymerizable units each comprisea basic monomeric unit being a part of a polymer chain of the prepolymerand a pendant or terminal, ethylenically-unsaturated group attachedthereon, wherein each basic monomeric unit is derived from a firstethylenically functionalizing vinylic monomer having a second reactivefunctional group, wherein the pendant or terminal ethylenicallyunsaturated group is derived from a second ethylenically functionalizingvinylic monomer having a third reactive functional group which reactswith one second reactive functional in the presence or absence of acrosslinking agent to form a covalent linkage. The second and thirdreactive functional groups are selected from the group consisting ofamino group, hydroxyl group, carboxyl group, azlactone group, isocyanategroup, epoxy group, aziridine group, acid chloride, and combinationthereof. Examples of such vinylic monomers are those ethylenicallyfunctionalizing vinylic monomers described above. Preferably, the firstethylenically functionalizing vinylic monomer is any one of thosedescribed above.

In accordance with the invention, the content of the polymerizable unitsare determined based on weight percentage of the ethylenicallyfunctionalizing vinylic monomer present in the polymerizable compositionfor making an intermediary copolymer relative to the total weight ofpolymerizable components in the polymerizable composition or the weightpercentage of the ethylenically functionalizing vinylic monomer used inethylenically functionalizing the intermediary copolymer to form theprepolymer of the invention, relative to the weight of the prepolymer.

A chain transfer agent (containing at least one thiol group) is used tocontrol the molecular weight of the resultant intermediary copolymer.Where a chain transfer has a reactive functional group such as amine,hydroxyl, carboxyl, epoxy, isocyanate, azlactone, or aziridine group, itcan provide terminal or pendant functionality (amine, hydroxyl,carboxyl, epoxy, isocyanate, azlactone, or aziridine group) forsubsequent ethylenical functionalization of the resultant intermediarycopolymer.

In another preferred embodiment, a polymer of the invention is asilicone hydrogel material which is obtained by thermally or actinicallypolymerizing a polymerizable composition which preferably comprises aTRIS-containing vinylic monomer of formula (I) as defined above and/oran actinically-crosslinkable prepolymer of the invention as describedabove. A silicone hydrogel material of the invention preferably is thebulk material of a soft contact lens which is obtained by polymerizingthe polymerizable composition in a mold, wherein the contact lens has awater content of from about 20% to about 75% (preferably from about 25%to about 70%, more preferably from about 30% to about 65%) by weightwhen fully hydrated, an oxygen permeability (Dk) of at least about 40barrers (preferably at least about 50 barrers, more preferably at leastabout 60 barrers, and even more preferably at least about 70 barrers),and an elastic modulus of from about 0.1 MPa to about 2.0 MPa,preferably from about 0.2 MPa to about 1.5 MPa, more preferably fromabout 0.3 MPa to about 1.2 MPa, even more preferably from about 0.4 MPato about 1.0 MPa. The polymerizable composition for obtaining a softcontact lens of the invention can further comprise one or morecomponents selected from the group consisting of a hydrophilic vinylicmonomer (any one of those described above), a hydrophobic vinylicmonomer (any one of those described above), a polysiloxane-containingvinylic monomer (any one of those described above), apolysiloxane-containing crosslinker (any one of those described above),a non-silicone crosslinker (any one of those described above), aphotoinitiator (any one of those described above), a thermal initiator(any one of those described above), a UV-absorbing vinylic monomer (anyone of those described above), a visibility tinting agent (e.g., dyes,pigments, or mixtures thereof), antimicrobial agents (e.g., preferablysilver nanoparticles), a bioactive agent (e.g., rebamipide, ketotifen,olaptidine, cromoglycolate, cyclosporine, nedocromil, levocabastine,lodoxamide, ketotifen, or the pharmaceutically acceptable salt or esterthereof, 2-pyrrolidone-5-carboxylic acid, vitamins, or mixturesthereof), leachable lubricants (e.g., polyglycolic acid, a water-solublenon-crosslinkable hydrophilic polymer), leachable tear-stabilizingagents (e.g., phospholipids), and mixtures thereof.

Lens molds for making contact lenses are well known to a person skilledin the art and, for example, are employed in cast molding or spincasting. For example, a mold (for cast molding) generally comprises atleast two mold sections (or portions) or mold halves, i.e. first andsecond mold halves. The first mold half defines a first molding (oroptical) surface and the second mold half defines a second molding (oroptical) surface. The first and second mold halves are configured toreceive each other such that a lens forming cavity is formed between thefirst molding surface and the second molding surface. The moldingsurface of a mold half is the cavity-forming surface of the mold and indirect contact with lens-forming material.

Methods of manufacturing mold sections for cast-molding a contact lensare generally well known to those of ordinary skill in the art. Theprocess of the present invention is not limited to any particular methodof forming a mold. In fact, any method of forming a mold can be used inthe present invention. The first and second mold halves can be formedthrough various techniques, such as injection molding or lathing.Examples of suitable processes for forming the mold halves are disclosedin U.S. Pat. No. 4,444,711 to Schad; U.S. Pat. No. 4,460,534 to Boehm etal.; U.S. Pat. No. 5,843,346 to Morrill; and U.S. Pat. No. 5,894,002 toBoneberger et al., which are also incorporated herein by reference.

Virtually all materials known in the art for making molds can be used tomake molds for making contact lenses. For example, polymeric materials,such as polyethylene, polypropylene, polystyrene, PMMA, Topas® COC grade8007-S10 (clear amorphous copolymer of ethylene and norbornene, fromTicona GmbH of Frankfurt, Germany and Summit, N.J.), or the like can beused. Other materials that allow UV light transmission could be used,such as quartz glass and sapphire.

In accordance with the invention, the polymerizable composition can beintroduced (dispensed) into a cavity formed by a mold according to anyknown methods.

After the polymerizable composition is dispensed into the mold, it ispolymerized to produce a contact lens. Crosslinking may be initiatedthermally or actinically, preferably by exposing the lens-formingcomposition in the mold to a spatial limitation of actinic radiation tocrosslink the polymerizable components in the polymerizable composition.

Opening of the mold so that the molded article can be removed from themold may take place in a manner known per se.

The molded contact lens can be subject to lens extraction to removeunpolymerized polymerizable components. The extraction solvent can beany solvent known to a person skilled in the art. Examples of suitableextraction solvent are those described above. Preferably, water or anaqueous solution is used as extraction solvent. After extraction, lensescan be hydrated in water or an aqueous solution of a wetting agent(e.g., a hydrophilic polymer).

The molded contact lenses can further subject to further processes, suchas, for example, surface treatment, packaging in lens packages with apackaging solution which can contain about 0.005% to about 5% by weightof a wetting agent (e.g., a hydrophilic polymer described above or thelike known to a person skilled in the art) and/or a viscosity-enhancingagent (e.g., methyl cellulose (MC), ethyl cellulose,hydroxymethylcellulose, hydroxyethyl cellulose (HEC),hydroxypropylcellulose (HPC), hydroxypropylmethyl cellulose (HPMC), or amixture thereof); sterilization such as autoclave at from 118 to 124° C.for at least about 30 minutes; and the like.

The invention provides, in a further aspect, a method for preparing aTRIS-containing vinylic monomer of formula (I) as defined above. Amethod of the invention comprises the steps of: reacting apolyoxyethylene (meth)acrylate of formula (II) with an isocyanatoalkyltris(trimethylsiloxy)silane of formula (III)

in which R¹ is hydrogen or methyl, q1 is an integer of 6 to 20, and R₂is an alkyl, cycloalkyl or alkylcycloalkyl (preferrably alkyl) diradicalwith up to 20 carbon atoms which may have one or more ether, thio,amine, carbonyl, or amido linkages in the main chain (preferably, analkyl diradical with up to 12 carbon atoms), in the presence or absenceof a solvent and in the presence of a catalyst.

One known utilization of isocyanatoalkyl tris(trimethylsiloxy)silane isa cosmetic film-forming material obtained by reacting it with pullulan,as disclosed in JP-A H08-134103 (herein incorporated by reference in itsentirety). However, it is unknown to start with isocyanatoalkyltris(trimethylsiloxy)silane to produce a silicone methacrylate monomerhaving a desired water solubility or dispersibility and suitable formaking for contact lenses.

Polyoxyethylene monomethacrylate products based on the compound offormula (II) as defined above are commercially available under thetradename of, for example, HEMA-10 (q1=10) from BIMAX Chemicals Ltd.,Blemmer® PE350 (m=8) and Blemmer® PE450 (q1=10) from NOF Corp., MA-80A(q1=8) and MA-100A (q1=10) from Nippon Nyukazai Co., Ltd.

Polyoxyethylene mono-(meth)acrylate products based on the compound offormula (II) can be prepared by ring-opening polymerization reaction ofethylene oxide with hydroxyethyl (meth)acrylate (CH₂═CHC═OOCH₂CH₂OH(HEA) or CH₂═CCH₃C═OOCH₂CH₂OH (HEMA)) in the presence of an epoxyring-opening catalyst. The product is a mixture of the desired compound(II) with polyethylene glycol (HO(CH₂CH₂O)_(m)H) and polyoxyethylenedimethacrylate (CH₂═CR¹C═OO(CH₂CH₂O)_(q1)O═CCR¹═CH₂) formed asbyproducts by trans-esterification during polymerization reaction. It isnoted that R¹ is hydrogen or methyl and q1 is an integer of 6 to 20. Inthis context, the product is designated II′, hereinafter.

The step of reacting II′ with isocyanatoalkyl tris(trimethylsiloxy)silane of formula (III) (e.g., tris(trimethylsiloxy)silylpropylisocyanate) may be carried out in a solvent although the reaction mayproceed even in a solventless system. The solvent, if used, ispreferably selected from ketone solvents such as methyl ethyl ketone(MEK) and methyl isobutyl ketone (MIBK).

The catalyst used for the reaction is preferably selected from aminecatalysts such as triethylamine, tin catalysts such as dibutyltindilaurate, and iron catalysts such as tris(2,4-pentanedionato)iron(III).Of these, the iron catalysts are most preferred for low toxicity becausethe amine compounds have a low catalytic activity and the tin catalystsare toxic despite high activity. The catalyst is preferably used in anamount of about 10 to about 1,000 ppm, more preferably about 50 to about500 ppm based on the total weight of II′ and isocyanatoalkyltris(trimethylsiloxy) silane of formula (III).

The reacting step may be carried out by charging II′, isocyanatoalkyltris(trimethylsiloxy) silane of formula (III) (e.g.,tris(trimethylsiloxy)silylpropyl isocyanate) and a reaction solvent in areactor and adding a catalyst thereto. In the preferred procedure, areactor is charged with II′, solvent and catalyst, whereuponisocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) (e.g.,tris(trimethylsiloxy)silylpropyl isocyanate) is added dropwise.Preferably, dropwise addition is started at a temperature of about −10°C. to about 30° C., and the internal temperature of the reaction mixtureis controlled below 50° C. during dropwise addition. The reactiontemperature is preferably controlled in a range of about −10° C. toabout 120° C., more preferably 20 to 50° C. On IR (infra red)monitoring, the end of reaction is detected when the peaks assigned toisocyanate group are extinguished from the IR chart. For example, thereaction is completed within about 3 hours at a reaction temperature ofabout 40° C. (as shown in the Examples).

For reaction, II′ and isocyanatoalkyl tris(trimethylsiloxy) silane offormula (III) (e.g., tris(trimethylsiloxy)silylpropyl isocyanate) may beused in an arbitrary molar ratio. However, it is unfavorable to useisocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) (e.g.,tris(trimethylsiloxy)silylpropyl isocyanate) in a molar excess relativeto the moles of hydroxyl groups in II′ because isocyanate groups areleft behind and an alcohol or the like must be added to scavenge theresidual isocyanate. For this reason, II′ is preferably used in suchamounts that about 1.0 to about 1.2 moles of hydroxyl groups may beavailable per mole of isocyanatoalkyl tris(trimethylsiloxy) silane offormula (III) (e.g., tris(trimethylsiloxy)-silylpropyl isocyanate)(i.e., molar ratio of II′ to isocyanatoalkyl tris(trimethylsiloxy)silane of formula (III) being from about 1.0 to about 1.2). In II′, q1is an integer of 6 to 20, preferably an integer of 8 to 14.

Although various embodiments of the invention have been described usingspecific terms, devices, and methods, such description is forillustrative purposes only. The words used are words of descriptionrather than of limitation. It is to be understood that changes andvariations may be made by those skilled in the art without departingfrom the spirit or scope of the present invention, which is set forth inthe following claims. In addition, it should be understood that aspectsof the various embodiments may be interchanged either in whole or inpart or can be combined in any manner and/or used together. Therefore,the spirit and scope of the appended claims should not be limited to thedescription of the preferred versions contained therein.

The previous disclosure will enable one having ordinary skill in the artto practice the invention. In order to better enable the reader tounderstand specific embodiments and the advantages thereof, reference tothe following non-limiting examples is suggested. However, the followingexamples should not be read to limit the scope of the invention.

EXAMPLE 1 Oxygen Permeability Measurements.

The apparent oxygen permeability of a lens and oxygen transmissibilityof a lens material is determined according to a technique similar to theone described in U.S. Pat. No. 5,760,100 and in an article by Wintertonet al., (The Cornea: Transactions of the World Congress on the Cornea111, H. D. Cavanagh Ed., Raven Press: New York 1988, pp 273-280), bothof which are herein incorporated by reference in their entireties.Oxygen fluxes (J) are measured at 34° C. in a wet cell (i.e., gasstreams are maintained at about 100% relative humidity) using a Dk1000instrument (available from Applied Design and Development Co., Norcross,Ga.), or similar analytical instrument. An air stream, having a knownpercentage of oxygen (e.g., 21%), is passed across one side of the lensat a rate of about 10 to 20 cm³/min., while a nitrogen stream is passedon the opposite side of the lens at a rate of about 10 to 20 cm³/min. Asample is equilibrated in a test media (i.e., saline or distilled water)at the prescribed test temperature for at least 30 minutes prior tomeasurement but not more than 45 minutes. Any test media used as theoverlayer is equilibrated at the prescribed test temperature for atleast 30 minutes prior to measurement but not more than 45 minutes. Thestir motor's speed is set to 1200±50 rpm, corresponding to an indicatedsetting of 400±15 on the stepper motor controller. The barometricpressure surrounding the system, P_(measured), is measured. Thethickness (t) of the lens in the area being exposed for testing isdetermined by measuring about 10 locations with a Mitotoya micrometerVL-50, or similar instrument, and averaging the measurements. The oxygenconcentration in the nitrogen stream (i.e., oxygen which diffusesthrough the lens) is measured using the DK1000 instrument. The apparentoxygen permeability of the lens material, Dk_(app), is determined fromthe following formula:

Dk _(app) =Jt/(P _(oxygen))

where J=oxygen flux [microliters O₂/cm²-minute]

P_(oxygen)=(P_(measured)−P_(water) vapor)=(% O₂ in air stream) [mmHg]=partial pressure of oxygen in the air stream

P_(measured)=barometric pressure (mm Hg)

P_(water) vapor=0 mm Hg at 34° C. (in a dry cell) (mm Hg)

P_(water) vapor=40 mm Hg at 34° C. (in a wet cell) (mm Hg)

t=average thickness of the lens over the exposed test area (mm)

Dk_(app) is expressed in units of barrers.

The apparent oxygen transmissibility (Dk/t) of the material may becalculated by dividing the apparent oxygen permeability (Dk_(app)) bythe average thickness (t) of the lens.

The above described measurements are not corrected for the so-calledboundary layer effect which is attributable to the use of a water orsaline bath on top of the contact lens during the oxygen fluxmeasurement. The boundary layer effect causes the reported value for theapparent Dk of a silicone hydrogel material to be lower than the actualintrinsic Dk value. Further, the relative impact of the boundary layereffect is greater for thinner lenses than with thicker lenses. The neteffect is that the reported Dk appear to change as a function of lensthickness when it should remain constant.

The intrinsic Dk value of a lens can be estimated based on a Dk valuecorrected for the surface resistance to oxygen flux caused by theboundary layer effect as follows.

Measure the apparent oxygen permeability values (single point) of thereference lotrafilcon A (Focus® N&D® from CI BA VISION CORPORATION) orlotrafilcon B (AirOptix™ from CIBA VISION CORPORATION) lenses using thesame equipment. The reference lenses are of similar optical power as thetest lenses and are measured concurrently with the test lenses.

Measure the oxygen flux through a thickness series of lotrafilcon A orlotrafilcon B (reference) lenses using the same equipment according tothe procedure for apparent Dk measurements described above, to obtainthe intrinsic Dk value (Dk,) of the reference lens. A thickness seriesshould cover a thickness range of approximately 100 μm or more.Preferably, the range of reference lens thicknesses will bracket thetest lens thicknesses. The Dk_(app) of these reference lenses must bemeasured on the same equipment as the test lenses and should ideally bemeasured contemporaneously with the test lenses. The equipment setup andmeasurement parameters should be held constant throughout theexperiment. The individual samples may be measured multiple times ifdesired.

Determine the residual oxygen resistance value, R_(r), from thereference lens results using equation 1 in the calculations.

$\begin{matrix}{R_{r} = \frac{\sum\left( {\frac{t}{{Dk}_{app}} - \frac{t}{{Dk}_{i}}} \right)}{n}} & (1)\end{matrix}$

in which t is the thickness of the test lens (i.e., the reference lenstoo), and n is the number of the reference lenses measured. Plot theresidual oxygen resistance value, R_(r) vs. t data and fit a curve ofthe form Y=a+bX where, for the jth lens, Y_(j)=(ΔP/J)_(j) and X=t_(j).The residual oxygen resistance, R_(r) is equal to a.

Use the residual oxygen resistance value determined above to calculatethe correct oxygen permeability Dk_(c) (estimated intrinsic Dk) for thetest lenses based on Equation 2.

Dk _(c) =t/[(t/Dk _(a))−R _(r)]  (2)

The estimated intrinsic Dk of the test lens can be used to calculatewhat the apparent Dk (Dk_(a) _(_) _(std)) would have been for a standardthickness lens in the same test environment based on Equation 3. Thestandard thickness (t_(std)) for lotrafilcon A=85 μm. The standardthickness for lotrafilcon B=60 μm.

Dk _(a) _(_) _(std) =t _(std)/[(t _(std) /Dk _(c))+R _(r) _(_)_(std)]  (3)

Ion Permeability Measurements.

The ion permeability of a lens is measured according to proceduresdescribed in U.S. Pat. No. 5,760,100 (herein incorporated by referencein its entirety. The values of ion permeability reported in thefollowing examples are relative ionoflux diffusion coefficients(D/D_(ref)) in reference to a lens material, Alsacon, as referencematerial. Alsacon has an ionoflux diffusion coefficient of 0.314×10⁻³mm²/minute.

EXAMPLE 2 Synthesis of Monomer (1A)

A 2-L flask equipped with a Dimroth condenser, thermometer and droppingfunnel is charged with 471 g (1.1 mol) of MA-80A (q1=8, Nippon NyukazaiCo., Ltd., hydroxyl number 131 mg KOH/g, polyethyleneglycol/polyoxyethylene dimethacrylate/II=5/10/85), 0.09 g (100 ppm basedon reactants) of tris(2,4-pentanedionato)iron(III) as urethane-formingcatalyst, and 800 g of methyl ethyl ketone as solvent. The flask isheated at 30° C. whereupon 379 g (1 mol) oftris(trimethylsiloxy)silylpropyl isocyanate is added dropwise from thedropping funnel over one hour. At this point, the internal temperaturerises to 40° C. Reaction is continued at an internal temperature of35-45° C. for 3 hours. On IR analysis, the consumption of isocyanategroup is confirmed. Silica gel, 170 g, is added to the reactionsolution, which is stirred for one hour for decoloring. The silica gelis filtered off, and the solvent, MEK is distilled off in vacuum at aninternal temperature of 60° C., yielding 578 g of Monomer (1A)(polyoxyethylene methacrylate of formula (II) in which q1 is 8, R₁ ismethyl, and R₂ is —CH₂CH₂CH₂—).

Synthesis of Monomer (1B)

Reaction is carried out as above for synsthsizing Monomer (1A) exceptthat 556 g (1.1 mol) of MA-100A (q1=10, Nippon Nyukazai Co., Ltd.,polyethylene glycol/polyoxyethylene dimethacrylate/II=6/14/80) was usedinstead of MA-80A. After decoloring, the solvent, MEK was distilled offin vacuum at 60° C., yielding 655 g of Monomer (1B) (polyoxyethylenemethacrylate of formula (II) in which q1 is 10, R₁ is methyl, and R₂ is—CH₂CH₂CH₂—).

Characterization of TRIS-Containing Vinylic Monomer

Monomer (1A) is a colorless transparent liquid having a viscosity of 123mm²/s at 25° C., a refractive index of 1.4477 at 25° C., and a purity of94% as determined by liquid chromatography.

Monomer (1B) is a colorless transparent liquid having a viscosity of 119mm²/s at 25° C., a refractive index of 1.4493 at 25° C., and a purity of89% as determined by liquid chromatography. FIG. 1 is a diagram showingthe ¹H-NMR spectrum of Monomer (1B).

EXAMPLE 3 Synthesis of Macromers

Macromers are synthesized according to the following procedures insubstantial accordance with teachings in Example B-1 to B-4 of U.S. Pat.No. 5,849,811.

51.5 g (50 mmol) of the perfluoropolyether Fomblin® ZDOL (from AusimontS.p.A, Milan) having a mean molecular weight of 1030 g/mol andcontaining 1.96 meq/g of hydroxyl groups according to end-grouptitration is introduced into a three-neck flask together with 50 mg ofdibutyltin dilaurate. The flask contents are evacuated to about 20 mbarwith stirring and subsequently decompressed with argon. This operationis repeated twice. 22.2 g (0.1 mol) of freshly distilled isophoronediisocyanate kept under argon are subsequently added in a counterstreamof argon. The temperature in the flask is kept below 30° C. by coolingwith a waterbath. After stirring overnight at room temperature, thereaction is complete. Isocyanate titration gives an NCO content of 1.40meq/g (theory: 1.35 meq/g).

202 g of the a,co-hydroxypropyl-terminated polydimethylsiloxane KF-6001from Shin-Etsu having a mean molecular weight of 2000 g/mol (1.00 meq/gof hydroxyl groups according to titration) are introduced into a flask.The flask contents are evacuated to approx. 0.1 mbar and decompressedwith argon. This operation is repeated twice. The degassed siloxane isdissolved in 202 ml of freshly distilled toluene kept under argon, and100 mg of dibutyltin dilaurate (DBTDL) are added. After completehomogenization of the solution, all the perfluoropolyether reacted withisophorone diisocyanate (IPDI) is added under argon. After stirringovernight at room temperature, the reaction is complete. The solvent isstripped off under a high vacuum at room temperature. Microtitrationshows 0.36 meq/g of hydroxyl groups (theory 0.37 meq/g).

13.78 g (88.9 mmol) of 2-isocyanatoethyl methacrylate (IEM) are addedunder argon to 247 g of the α,σ-hydroxypropyl-terminatedpolysiloxane-perfluoropolyether-polysiloxane three-block copolymer (athree-block copolymer on stoichiometric average, but other block lengthsare also present). The mixture is stirred at room temperature for threedays. Microtitration then no longer shows any isocyanate groups(detection limit 0.01 meq/g). 0.34 meq/g of methacryl groups are found(theory 0.34 meq/g).

The macromer prepared in this way is completely colourless and clear. Itcan be stored in air at room temperature for several months in theabsence of light without any change in molecular weight.

EXAMPLE 4

Lens formulations are prepared from the macromere prepared in Example 3,Monomer (1A) prepared in Example 2, N,N-dimethylacrylamide (DMA),solvent (1-propanol—1-PrOH or ethanol—Et-OH), photoinitiator(Darocur®1173 from Ciba Chemicals) to have the compositions shown inTable 1. All the concentrations of the components are weight percentage(% w/w).

The photorheology of the prepared lens formulation is studied and theresults are reported in Table 1.

To make lenses, a lens formulation prepared above is pipetted intodust-free contact-lens molds made from polypropylene. The molds areclosed, and the polymerization reaction is effected by UV irradiation(5.0 mW/cm², 30 minutes), with simultaneous crosslinking. The molds arethen opened and placed in isopropanol, causing the resultant lenses toswell out of the molds. The lenses are extracted for 4 hours minimumwith 100% isopropyl alcohol before being placed into water. The lensesare coated and finally equilibrated in phosphate-buffered physiologicalsaline solution in specially designed foil packages and then autoclavedat 120° C. for 30 minutes. The obtained lenses are characterized and thephysical and mechanical properties (oxygen permeability—Dkc, ionpermeability—IP, water content at equilibrium—% w/w, elastic modulusE′—Mpa, elongation at break—EtB %) are reported in Table 1.

TABLE 1 Formulation Components RD-5399-073A0 RD-5399-073A4 Macromer 31%29% Monomer (1A) 18% 16% DMA 26% 30% 1-PrOH 24% — Et—OH — 24% DC1173  1% 1% Photorheology Curing Time 29 sec 32 sec G′ 230 kPa  215 kPa Viscosity    16 mPa · s    11 mPa · s Lens Proeprties Water Content %38.4%   42.3%   Dkc 70 57 IP 13 16 E′ (MPa) 1.16 1.08 EtB % 165 78

1-7. (canceled)
 8. A method for preparing a silicone vinylic monomer, comprising the steps of: reacting a polyoxyethylene (meth)acrylate of formula (II) with an isocyanatoalkyl tris(trimethylsiloxy)silane of formula (III) in the presence or absence of a solvent and in the presence of a catalyst to form the silicone vinylic monomer of formula (I),

wherein R¹ is hydrogen or methyl, q1 is an integer of 6 to 20, and R₂ is a diradical of an alkane or cycloalkane which comprises up to 20 carbon atoms and may have one or more ether, thio, amine, carbonyl, or amido linkages in the main chain.
 9. The method of claim 8, wherein the step of reacting is carried out in a solvent that is a ketone solvent.
 10. The method of claim 8, wherein the catalyst is an amine catalysts, a tin catalyst, and/or an iron catalyst.
 11. The method of claim 8, wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).
 12. The method of claim 8, wherein the step of reacting is carried out by charging the polyoxyethylen (meth)acrylate of formula (II), the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) and a reaction solvent in a reactor and then adding a catalyst thereto to form a reaction mixture.
 13. The method of claim 8, wherein the step of reacting is carried out by charging the polyoxyethylen (meth)acrylate of formula (II), a reaction solvent and a catalyst in a reactor, whereupon the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) is added dropwise to form a reaction mixture, wherein the dropwise addition is started at a temperature of about −10° C. to about 30° C., and the internal temperature of the reaction mixture is controlled below 50° C. during dropwise addition.
 14. The method of claim 8, wherein the molar ratio of polyoxyethylene (meth)acrylate of formula (II) to isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) is from about 1.0 to about 1.2.
 15. The method of claim 9, wherein the step of reacting is carried out in a solvent that is a ketone solvent selected from methyl ethyl ketone and methyl isobutyl ketone.
 16. The method of claim 8, wherein the catalyst is selected from the group consisting of triethylamine, dibutyltin dilaurate, tris(2,4-pentanedionato)iron(III), and combinations thereof.
 17. The method of claim 9, wherein the catalyst is selected from the group consisting of triethylamine, dibutyltin dilaurate, tris(2,4-pentanedionato)iron(III), and combinations thereof.
 18. The method of claim 15, wherein the catalyst is selected from the group consisting of triethylamine, dibutyltin dilaurate, tris(2,4-pentanedionato)iron(III), and combinations thereof.
 19. The method of claim 9, wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).
 20. The method of claim 10, wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).
 21. The method of claim 15, wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).
 22. The method of claim 16, wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).
 23. The method of claim 17, wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).
 24. The method of claim 18, wherein the catalyst is present in an amount of about 10 to about 1,000 ppm based on the total weight of the polyoxyethylene (meth)acrylate of formula (II) and the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III).
 25. The method of claim 18, wherein the step of reacting is carried out by charging the polyoxyethylen (meth)acrylate of formula (II), the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) and a reaction solvent in a reactor and then adding a catalyst thereto to form a reaction mixture.
 26. The method of claim 18, wherein the step of reacting is carried out by charging the polyoxyethylen (meth)acrylate of formula (II), a reaction solvent and a catalyst in a reactor, whereupon the isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) is added dropwise to form a reaction mixture, wherein the dropwise addition is started at a temperature of about −10° C. to about 30° C., and the internal temperature of the reaction mixture is controlled below 50° C. during dropwise addition.
 27. The method of claim 18, wherein the molar ratio of polyoxyethylene (meth)acrylate of formula (II) to isocyanatoalkyl tris(trimethylsiloxy) silane of formula (III) is from about 1.0 to about 1.2. 